Tree-flower-shaped nickel-based amorphous composite material as well as preparation method and application thereof

Abstract

The invention discloses a tree-flower-shaped nickel-based amorphous composite material as well as a preparation method and application thereof, and belongs to the field of seawater electro-catalysis. The tree-flower-shaped nickel-based amorphous composite material comprises a NiM amorphous alloy wire, wherein M is composed of a transition metal element and a non-metal element; the NiM amorphous alloy wire comprises a NiM amorphous alloy wire and NiBPNOx nanoflowers, the outermost layer of the NiBPNOx nanoflowers is of an amorphous NiOx structure, the NiBPNOx nanoflowers are combined on the surface of the NiM amorphous alloy wire, and x refers to the content of oxygen elements. According to the structure, an amorphous alloy wire serves as a precursor, the outer layer of the amorphous alloy wire is wrapped with a NiBPNOx nanoflower structure, and the whole structure is of a tree-flower-shaped structure. The prepared tree-flower-shaped nickel-based amorphous composite material has the characteristics of high corrosion resistance, large surface area and high activity, and has excellent and stable hydrogen production performance in seawater electrocatalysis as an electrocatalyst. In addition, the preparation method provided by the invention is convenient and rapid, has strong industrialization, and provides good technical basis and material guarantee for seawater electrolysis hydrogen production application.

Description

Technical Field

[0001] The present invention relates to the field of electrocatalysis of seawater, and particularly to a dendritic nickel-based amorphous composite material, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, hydrogen energy as a clean energy carrier has attracted much attention. Among them, the hydrogen production technology based on electrocatalytic water splitting (especially the direct electrolysis of seawater to produce hydrogen) provides an important way to solve the energy crisis and promote the development of new energy. At present, the research focus is on noble metal catalysts (such as platinum, iridium, etc.). These materials exhibit excellent hydrogen evolution reaction (HER) activity due to their ideal hydrogen adsorption free energy. However, their high cost and scarce reserves seriously restrict the large-scale application process.

[0003] In the non-noble metal catalyst system, transition metal elements such as Ni, Fe, Co, etc. show the potential to replace noble metal catalysts due to their rich reserves and strong adjustability of electronic structures. However, current research shows that the existing catalysts for seawater still have bottleneck problems such as easy corrosion in seawater and low density of active sites, which leads to a significant gap between their electrocatalytic performance in the seawater environment and the actual requirements. Currently, amorphous materials have become catalytic materials that have attracted much attention due to their high density of unsaturated coordination degrees and low catalytic activation energy. However, in the field of electrocatalysis of seawater, the synergistic catalytic mechanism between transition metal multi-component compositions and amorphous short- to medium-range structures has not been fully studied, and there is still a lack of systematic exploration in terms of corrosion resistance, long-term stability, and high catalytic activity. At the same time, there is also a need for breakthroughs in the synthesis strategy and structural design methodology of amorphous materials. Summary of the Invention

[0004] In view of the above deficiencies of the prior art, the purpose of the present invention is to provide a dendritic nickel-based amorphous composite material, a preparation method thereof, and an application thereof, aiming to solve the problems such as easy corrosion in seawater and low density of active sites existing in the current electrocatalysts for seawater electrolysis to produce hydrogen.

[0005] The purpose of the present invention is to develop an electrocatalyst that not only has excellent corrosion resistance, high activity and stability, but also has cost-effectiveness, and to establish a new paradigm for the design of electrocatalysts for seawater electrolysis applications, so as to promote the industrial development of green hydrogen production technology from marine resources.

[0006] The technical solution of the present invention is as follows:

[0007] In the first aspect of the present invention, a dendritic nickel-based amorphous composite material is provided, wherein the dendritic nickel-based amorphous composite material (which can be denoted as NiBPNO x @NiM dendritic nickel-based amorphous composite material) includes:

[0008] NiM amorphous alloy wire, where M is composed of transition metal elements and non-metal elements;

[0009] NiBPNO x nanoflowers, said NiBPNO x The outermost layer of the nanoflowers is amorphous NiO x structure, said NiBPNO x The nanoflowers are bonded to the surface of the NiM amorphous alloy wire, where x refers to the content of oxygen element.

[0010] Optionally, the transition metal element is selected from at least one of Fe, Co, Mo, and Nb, and the non-metal element is selected from at least one of Si, P, B, and C.

[0011] Optionally, the NiM is selected from one of NiFeP, NiMoPFe, NiCoFeP, and NiFeCoPMo.

[0012] Optionally, the cross-section of the NiM amorphous alloy wire is a circular cross-section, and the diameter of the circular cross-section is 50 - 120 μm.

[0013] Optionally, the atomic percentage of Ni in the NiM amorphous alloy wire > 30%.

[0014] In the second aspect of the present invention, there is provided a method for preparing the dendritic nickel-based amorphous composite material of the present invention, which includes the steps:

[0015] Provide NiM amorphous alloy wire, where M is composed of transition metal elements and non-metal elements;

[0016] Deposit NiBPNO x nanoflowers on the surface of the NiM amorphous alloy wire by chemical deposition to obtain the dendritic nickel-based amorphous composite material.

[0017] Optionally, the NiM amorphous alloy wire is prepared by the following method:

[0018] Mix the raw materials corresponding to the target product NiM amorphous alloy wire to obtain a mixed raw material;

[0019] Adopt the vacuum arc melting - copper mold suction casting technology to prepare the mixed raw material into a rod;

[0020] Put the rod into a glass tube, heat the rod so that a layer of glass tube wraps the outer surface of the rod;

[0021] Cool the rod wrapped with the glass tube to obtain the NiM amorphous alloy wire wrapped with the glass tube;

[0022] The NiM amorphous alloy wire wrapped with the glass tube is immersed in hydrofluoric acid to remove the glass tube on the outer surface of the NiM amorphous alloy wire, thereby obtaining the NiM amorphous alloy wire.

[0023] Optionally, the step of depositing NiBPNO x nanoflowers on the surface of the NiM amorphous alloy wire by chemical deposition method specifically includes:

[0024] The NiM amorphous alloy wire is immersed in a mixed solution containing NiCl2·6H2O, sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O) and polyvinylpyrrolidone, and then sodium borohydride is added to obtain a reaction system;

[0025] The reaction system is reacted under an inert atmosphere to deposit NiBPNO x nanoflowers on the surface of the NiM amorphous alloy wire; wherein, the reaction temperature is 25 - 50 °C, the solution needs to be circulated by a peristaltic pump, and its flow rate is 5 - 9 mL / min, and the reaction time is 0.5 - 3 hours.

[0026] Optionally, the concentration of NiCl2·6H2O in the mixed solution is 0.2 - 0.6 mol / L, the mass of sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O) is 6.5 - 8.2 g / L, and the mass of polyvinylpyrrolidone is 0.1 - 0.5 g / L.

[0027] In the third aspect of the present invention, there is provided a dendritic nickel-based amorphous composite material as described in the present invention for use in electrocatalytic hydrogen production from seawater electrolysis.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] NiBPNO x @NiM is a three-layer composite amorphous dendritic structure, and the nickel-based amorphous composite material of this structure exhibits very high catalytic activity, which is reflected in that when the current density j = 1000 mA / cm 2 during the simulated seawater electrolysis overall hydrolysis process (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, and the electrolyte is 1M KOH + 0.5M NaCl solution), the cell voltage is 1.68 - 1.88 V, and during the actual seawater electrolysis overall hydrolysis process (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, and the electrolyte is 1M KOH + real seawater), the cell voltage is 1.82 - 1.95 V.

[0030] In addition, NiBPNO x@The NiM dendritic nickel-based amorphous composite material exhibits very good corrosion resistance in seawater, which is reflected in a very wide passivation range.

[0031] In addition, NiBPNO x @The preparation method of the NiM dendritic nickel-based amorphous composite material is convenient and fast, and has strong industrialization, providing a good technical foundation and material guarantee for the application of hydrogen production by seawater electrolysis. Description of the Drawings

[0032] Figure 1 It is a schematic diagram of the preparation process of the dendritic nickel-based amorphous composite material in a specific embodiment of the present invention.

[0033] Figure 2 It is an atomic microscopic structure diagram of the dendritic nickel-based amorphous composite material under a transmission electron microscope in a specific embodiment of the present invention.

[0034] Figure 3 It is a corrosion resistance performance diagram of the dendritic nickel-based amorphous composite material in a specific embodiment of the present invention.

[0035] Figure 4 It is an electrolyzed water performance diagram of the dendritic nickel-based amorphous composite material in a specific embodiment of the present invention. Detailed Embodiments

[0036] The present invention provides a dendritic nickel-based amorphous composite material and its preparation method and application. To make the purpose, technical solution and effect of the present invention clearer and more definite, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0037] In one embodiment, a dendritic nickel-based amorphous composite material is provided, wherein the dendritic nickel-based amorphous composite material includes:

[0038] NiM amorphous alloy wire, wherein M is composed of transition metal elements and non-metal elements;

[0039] NiBPNO x nanoflowers, the outermost layer of the NiBPNO x nanoflowers is an amorphous NiO x structure, the NiBPNO x nanoflowers are combined on the surface of the NiM amorphous alloy wire, where x refers to the content of oxygen element.

[0040] In this embodiment, the NiM amorphous alloy wire serves as the trunk, and the surface of the NiM amorphous alloy wire is wrapped with a layer of amorphous NiBPNO x nanoflowers, and the outermost layer of the nanoflowers is amorphous NiOx The structure presents an overall dendritic structure. Therefore, the dendritic nickel-based amorphous composite material is also denoted as NiBPNO x @NiM dendritic nickel-based amorphous composite material. This dendritic nickel-based amorphous composite material has the characteristics of strong corrosion resistance, large surface area, and high activity. As an electrocatalyst, it has excellent and stable hydrogen production performance in seawater electrocatalysis. In addition, the preparation method of this dendritic nickel-based amorphous composite material is convenient and fast, and has strong industrialization, providing a good technical foundation and material guarantee for the application of seawater electrolysis for hydrogen production.

[0041] In one embodiment, the transition metal element is selected from at least one of Fe, Co, Mo, Nb, etc., and the non-metal element is selected from at least one of Si, P, B, C, etc.

[0042] In one embodiment, the NiM is selected from one of NiFeP, NiMoPFe, NiCoFeP, NiFeCoPMo.

[0043] In one embodiment, the NiM amorphous alloy wire has a uniform thickness, a smooth, clean, and defect-free surface.

[0044] In one embodiment, the cross-section of the NiM amorphous alloy wire is a circular cross-section, and the diameter of the circular cross-section is 50 - 120 μm, such as 50 μm, 70 μm, 90 μm, 100 μm, 120 μm, etc. The diameter of the circular cross-section can be controlled by adjusting the drawing speed (v, rad / min).

[0045] In one embodiment, the atomic percentage of Ni in the NiM amorphous alloy wire > 30%, such as 40%, 50%, 60%, 70%, 80%, etc. At this ratio, the Ni element is beneficial to ensuring the catalytic activity of the electrocatalyst.

[0046] In one embodiment, a preparation method of the dendritic nickel-based amorphous composite material, wherein, includes the steps:

[0047] S1. Provide a NiM amorphous alloy wire, where M is composed of a transition metal element and a non-metal element;

[0048] S2. Deposit NiBPNO x nanoflowers on the surface of the NiM amorphous alloy wire to obtain the dendritic nickel-based amorphous composite material.

[0049] In one embodiment, the NiM amorphous alloy wire is prepared by the following method:

[0050] Mix the raw materials corresponding to the target product NiM amorphous alloy wire to obtain a mixed raw material;

[0051] Using the vacuum arc melting - copper mold suction casting technology, the mixed raw materials are prepared into rods.

[0052] Put the rod into a glass tube, heat the rod, so that a layer of glass tube wraps the outer surface of the rod.

[0053] Cool the rod wrapped with the glass tube to obtain a NiM amorphous alloy wire wrapped with the glass tube.

[0054] Immerse the NiM amorphous alloy wire wrapped with the glass tube in hydrofluoric acid to remove the glass tube on the outer surface of the NiM amorphous alloy wire, and obtain the NiM amorphous alloy wire.

[0055] Specifically, through the calculation of the mixing enthalpy between multiple groups of elements, the NiM (also known as Ni - based) amorphous alloy elements with excellent amorphous - forming ability are determined. Among them, the Ni element is the main element (>30 at.%), and M is an amorphous alloy element composed of a combination of transition metal elements (such as Fe, Co, Mo, Nb, etc.) and non - metal elements (such as Si, P, B, C, etc.). Using the vacuum arc melting - copper mold suction casting technology, the mixed raw materials are prepared into rods (the diameter of the rods can be 3 - 7 mm). Then put the rods into a special high - softening - point glass tube (with a thickness of 2 - 3 mm and a softening point of 1200 - 1300 °C), and rapidly heat the rods through a high - frequency induction heating device controlled by a voltage of kilohertz. During the heating process, the applied voltage is 3 - 5 V to ensure that the heating temperature reaches 1200 - 1400 °C. Then apply a tensile stress of about 1 - 3 N with a glass needle tip, and quickly cool the molten rod wrapped with the softened glass tube in a coolant (the temperature can be about 0 °C) into a NiM amorphous alloy wire, and complete the large - batch preparation with the wire - winding bearing. Further, immerse the NiM amorphous alloy wire wrapped with the glass tube in hydrofluoric acid with a certain concentration (the concentration of hydrofluoric acid is 10 - 40 wt.%), and perform ultrasonic treatment (the power of ultrasonic treatment can be 90 - 100%). Remove the surface glass layer by ultrasonic immersion (the time can be 30 - 60 s). Then clean the surface residue with clean water and anhydrous ethanol, and dry it for standby.

[0056] In this embodiment, the circular cross - sectional diameter of the NiM amorphous alloy wire can be adjusted and controlled by the melting pool temperature T0 (K), the speed of the wire - drawing rate (v, rad / min), and the force (F) balance state in the glass - coating method.

[0057] In one embodiment, NiBPNO x nanoflowers are deposited on the surface of the NiM amorphous alloy wire by chemical deposition method, and the specific steps include:

[0058] The NiM amorphous alloy wire was immersed in a mixed solution containing NiCl2·6H2O, sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O), and polyvinylpyrrolidone (PVP), and then sodium borohydride (NaBH4, as a reducing agent, with a concentration of 0.5 - 1.2 mol / L in the mixed solution) was added to obtain a reaction system;

[0059] The reaction system was reacted under an inert atmosphere (such as nitrogen), and NiBPNO x nanoflowers were deposited on the surface of the NiM amorphous alloy wire; where the reaction temperature was 25 - 50 °C, the reaction system needed to be circulated through a peristaltic pump with a flow rate of 5 - 9 mL / min, and the reaction time was 0.5 - 3 hours.

[0060] In this example, using the NiM amorphous alloy wire as a substrate, NiBPNO x @NiM nickel-based amorphous composite material, namely NiBPNO x @NiM dendritic nickel-based amorphous composite material was designed with a dendritic structure through surface nanoengineering. And by chemical deposition method, using the NiM amorphous alloy wire as a substrate, NiBPNO x @NiM dendritic nickel-based amorphous composite material was prepared.

[0061] Among them, amorphous NiBPNO x nanoflowers were formed as follows:

[0062] Ni 2+ +NaH2PO2·H2O+NaBH4+H2O+PVP→NiBPNO x +B(OH)3+H2↑

[0063] Since B element participated in the reaction and was incorporated into the product during the reaction process, and the surface of the nanoflowers was easily modified by oxygen in deionized water and the surfactant PVP (containing nitrogen), the product was named NiBPNO x .

[0064] In this example, before depositing NiBPNO x nanoflowers on the surface of the NiM amorphous alloy wire, the surface of the NiM amorphous alloy wire can be first cleaned.

[0065] In this example, the reaction does not need to be carried out under stirring. After the reaction is completed, the reaction system can be thoroughly washed with deionized water and absolute ethanol, and then dried in a constant temperature vacuum oven at 40 - 60 °C for 10 - 20 hours to obtain pure NiBPNO x @NiM dendritic nickel-based amorphous composite material.

[0066] In one embodiment, a mixed solution containing NiCl2·6H2O, sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O), and polyvinylpyrrolidone is composed of NiCl2·6H2O, sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O), polyvinylpyrrolidone, and deionized water. The concentration of NiCl2·6H2O in the mixed solution is 0.2 - 0.6 mol / L, the mass of sodium dihydrogen phosphate monohydrate (NaH2PO2·H2O) in the mixed solution is 6.5 - 8.2 g / L, and the mass of polyvinylpyrrolidone is 0.1 - 0.5 g / L.

[0067] In one embodiment, one of the dendritic nickel-based amorphous composites is used as an electrocatalyst for hydrogen production by seawater electrolysis.

[0068] In this embodiment, NiBPNO x @NiM dendritic nickel-based amorphous composite can be used for hydrogen production by seawater electrolysis catalysis. This NiBPNO x @NiM dendritic nickel-based amorphous composite has very good corrosion resistance in seawater, which is reflected in having a very broad passivation range. Additionally, NiBPNO x @NiM dendritic nickel-based amorphous composite has very high catalytic activity, which is reflected in that when the current density j = 1000 mA / cm 2 during the simulated seawater electrolysis overall hydrolysis process (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, 1M KOH + 0.5M NaCl solution), the cell voltage is 1.68 - 1.88 V, and during the actual seawater electrolysis overall hydrolysis process (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, 1M KOH + real seawater), the cell voltage is 1.82 - 1.95 V.

[0069] The present invention will be further described in detail below through specific embodiments.

[0070] This embodiment provides a corrosion-resistant dendritic nickel-based amorphous composite and its preparation method and application. In this embodiment, NiM is NiFeP, and the NiFeP amorphous alloy wire is of uniform thickness, with a smooth, clean, and defect-free surface.

[0071] 1. As shown in a, b, c, and d in Figure 1 this embodiment, the preparation method of the NiBPNO x @NiFeP dendritic nickel-based amorphous composite includes the following steps:

[0072] Preparation of NiFeP amorphous alloy wire: By calculating the mixing enthalpy between multiple groups of elements, the NiM amorphous alloy elements with excellent amorphous formation ability are determined. NiM is NiFeP, where the atomic percentage of Ni is 60 at.%. Using the vacuum arc melting - copper mold suction casting technique, the mixed raw materials are prepared into rods with a circular cross - section diameter of 5 mm. Then the rods ( Figure 1 the alloy in) are placed in a special high - softening - point glass test tube (with a thickness of 2 mm and a softening point of 1200 °C), and the rods are rapidly heated by a high - frequency induction heating device (i.e., the heating coil) controlled by a voltage of kilohertz. During the heating process, the applied voltage is 3.5 V to ensure that the heating temperature reaches 1350 °C. Then, a tensile stress of about 1 N is applied using a glass needle tip, and the molten rods wrapped by the softened glass tube are rapidly cooled in a coolant at about 0 °C to form NiFeP amorphous alloy wires, and large - batch preparation is completed with the wire - winding bearing. The NiFeP amorphous alloy wires wrapped by the glass tube ( Figure 1 the glass - coated amorphous wire in) are immersed in a hydrofluoric acid solution with a concentration of 10 wt.%, and ultrasonic treatment (ultrasonic power is 90%) is carried out. By ultrasonic soaking for 50 s, the surface glass layer is removed. Then the surface residues are cleaned with clean water and absolute ethanol to obtain NiFeP amorphous alloy wires ( Figure 1 the amorphous alloy wire in), and they are dried for standby.

[0073] Chemical deposition: The prepared NiFeP amorphous alloy wires are placed in a mixed solution of 0.2 mol / L NiCl2·6H2O, 7.2 g / L NaH2PO2·H2O, and 0.1 g / L polyvinylpyrrolidone (PVP). A sodium borohydride solution (the concentration of NaBH4 in the mixed solution is 0.5 mol / L) is added as a reducing agent, and nitrogen is filled into the solution for reaction.

[0074] The temperature of the whole reaction is controlled at about 30 °C, the solution flow rate is 5 mL / min, and the reaction time is 0.5 hours. This reaction does not require stirring. After the reaction is completed, the reaction system is thoroughly cleaned with deionized water and absolute ethanol, and then dried in a constant - temperature vacuum oven at 40 °C for 10 hours to obtain NiBPNO x @NiFeP dendritic nickel - based amorphous composite material. The prepared NiBPNO x @NiFeP has a three - layer composite amorphous dendritic structure, as Figure 2 shown. The outer surface is an amorphous NiO x structure, the middle is NiBPNO x nanoflowers, and the bottom is NiFeP amorphous alloy wire.

[0075] 2. Complete NiBPNO xAfter the preparation of the dendritic nickel-based amorphous composite material of NiFeP, for NiBPNO x The dendritic nickel-based amorphous composite material of NiFeP was used as an electrocatalyst to test its corrosion resistance and the overall hydrolysis process of seawater electrolysis.

[0076] 1) Corrosion resistance test:

[0077] The three-electrode test was adopted for the corrosion resistance test: NiBPNO x @NiFeP, NiBPNO x and NiFeP were used as the anode materials respectively, Pt / C was used as the cathode material, and Hg / HgO was used as the reference electrode. The test environment was a simulated seawater solution (1M KOH + 0.5M NaCl solution). During the test, the scanning rate of the voltage was 5 mV / s, and the scanning range of the voltage was 1.0V - 1.7V.

[0078] NiBPNO x The corrosion resistance of the dendritic nickel-based amorphous composite material of NiFeP is as Figure 3 shown. The results show that NiBPNO x A layer of NiO on the surface of the dendritic nickel-based amorphous composite material of NiFeP x structure has very good corrosion resistance, which is reflected in the appearance of a broad passivation interval.

[0079] 2) Overall hydrolysis process test of seawater electrolysis:

[0080] The two-electrode test was adopted for the corrosion resistance test: NiBPNO x @NiFeP and the commercial catalyst IrO2 were used as the anode materials respectively, Pt / C was used as the cathode material, and the test environments were a simulated seawater solution (1M KOH + 0.5M NaCl solution) and a real seawater solution (1M KOH + real seawater). During the test, the scanning rate of the voltage was 5 mV / s, and the scanning range of the voltage was 1.2V - 2.0V. Before the test, cyclic voltammetry (CV) scanning 40 times was required to activate the electrocatalyst.

[0081] NiBPNO x The water electrolysis performance of the dendritic nickel-based amorphous composite material of NiFeP is as Figure 4 shown. The results show that during the overall hydrolysis process, NiBPNO x The dendritic nickel-based amorphous composite material of NiFeP as an electrocatalyst only requires a voltage of 1.77V to achieve a current density of 1000 mA / cm 2 in the simulated seawater solution environment, and the cell voltage during the actual overall hydrolysis process of the real seawater solution is 1.84V. The required voltage is much lower than that of the commercial catalyst.

[0082] In summary, a dendritic nickel-based amorphous composite material provided by the present invention, its preparation method and application, NiBPNO x @NiM is a three-layer composite amorphous dendritic structure. The nickel-based amorphous composite material with this structure exhibits very high catalytic activity, which is reflected in the current density j = 1000 mA / cm 2 When simulating the overall hydrolysis of seawater electrolysis (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, 1M KOH + 0.5M NaCl solution), the cell voltage is 1.77V. During the actual overall hydrolysis of seawater electrolysis (NiBPNO x @NiM as the anode material, Pt / C as the cathode material, 1M KOH + real seawater), the cell voltage is 1.845V. In addition, NiBPNO x @NiM dendritic nickel-based amorphous composite material shows very good corrosion resistance in seawater, which is reflected in a very wide passivation range. The preparation method of this material has convenient and fast conditions and strong industrialization, providing a good technical foundation and material guarantee for the application of seawater electrolysis for hydrogen production.

[0083] It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above description, and all such improvements and transformations should fall within the protection scope of the appended claims of the present invention.

Claims

1. A dendritic nickel-based amorphous composite material, characterized in that, The dendritic nickel-based amorphous composite material includes: NiM amorphous alloy wires, where M is composed of transition metal elements and non-metal elements; NiBPNO x nanoflowers, the NiBPNO x The outermost layer of the nanoflowers is amorphous NiO x structure, the NiBPNO x nanoflowers are combined on the surface of the NiM amorphous alloy wire, where x refers to the content of oxygen element.

2. The dendritic nickel-based amorphous composite material according to claim 1, wherein The transition metal elements are selected from at least one of Fe, Co, Mo, and Nb, and the non-metal elements are selected from at least one of Si, P, B, and C.

3. The dendritic nickel-based amorphous composite material according to claim 2, characterized in that The NiM is selected from one of NiFeP, NiMoPFe, NiCoFeP, and NiFeCoPMo.

4. The dendritic nickel-based amorphous composite material according to claim 1, wherein The cross-section of the NiM amorphous alloy wire is a circular cross-section, and the diameter of the circular cross-section is 50 - 120 μm.

5. The dendritic nickel-based amorphous composite material according to claim 1, characterized in that The atomic percentage of Ni in the NiM amorphous alloy wire > 30%.

6. A method for preparing the dendritic nickel-based amorphous composite material according to any one of claims 1-5, characterized in that, It includes the steps: Providing NiM amorphous alloy wires, where M is composed of transition group metal elements and non-metal elements; Deposit NiBPNO on the surface of the NiM amorphous alloy wire by chemical deposition method x nano-flowers to obtain the dendritic nickel-based amorphous composite material 7. The preparation method of the dendritic nickel-based amorphous composite material according to claim 6, characterized in that The NiM amorphous alloy wire is prepared by the following method: Mixing the raw materials corresponding to the target product NiM amorphous alloy wire to obtain a mixed raw material; Using the vacuum arc melting - copper mold suction casting technology to prepare the mixed raw material into a rod; Placing the rod in a glass tube and heating the rod so that a layer of glass tube wraps the outer surface of the rod; Cooling the rod wrapped with the glass tube to obtain the NiM amorphous alloy wire wrapped with the glass tube; Soaking the NiM amorphous alloy wire wrapped with the glass tube in hydrofluoric acid to remove the glass tube on the outer surface of the NiM amorphous alloy wire to obtain the NiM amorphous alloy wire.

8. The preparation method of the dendritic nickel-based amorphous composite material according to claim 6, characterized in that, The step of depositing NiBPNO nanowires on the surface of the NiM amorphous alloy wire by chemical deposition method specifically includes: x ​ Soaking the NiM amorphous alloy wire in a mixed solution containing NiCl2·6H2O, sodium dihydrogen phosphate monohydrate, and polyvinylpyrrolidone, and then adding sodium borohydride to obtain a reaction system; React the reaction system under an inert atmosphere to deposit NiBPNO on the surface of the NiM amorphous alloy wire x nanoflowers; wherein, the reaction temperature is 25 - 50 °C, the solution needs to be circulated by a peristaltic pump, the flow rate is 5 - 9 mL / min, and the reaction time is 0.5 - 3 hours.

9. The preparation method of the dendritic nickel-based amorphous composite material according to claim 8, characterized in that, The concentration of NiCl2·6H2O in the mixed solution is 0.2 - 0.6 mol / L, the mass of sodium dihydrogen phosphate monohydrate is 6.5 - 8.2 g / L, and the mass of polyvinylpyrrolidone is 0.1 - 0.5 g / L.

10. The dendritic nickel-based amorphous composite material according to any one of claims 1 - 5 is used as an electrocatalyst for hydrogen production by seawater electrolysis catalysis.

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